Catalytic conversion process



Patented Nov. 10, 1942 2,301,! 34 CATALYTIC CONVERSION PROCESS Ralph M. Melaven,

V. Shankland, Chicago,

and Oil Company, Chi

Indiana cago,

Highland; Ind., and Rodney assignors to Stand- 111., a corporation of No Drawing. Application December so, 1938, Serial No. 248,624

3 Claims.

This invention relates to the use of a crackin catalyst for the conversion of hydrocarbon oils and particularly to the conversion of heavy hydrocarbon oils such as gas oils, petroleum residuums, hydrocarbon waxes, etc., into lower boiling hydrocarbons, particularly gasoline. The invention relates more particularly to using catalysts for the'conversion of heavy hydrocarbon oils at high temperatures. One of the objects of the invention isto use a catalyst which will convert a larger amount of the oil into gasoline before it becomes necessary to regenerate it. Another object-of the invention is to use a catalyst which may be repeatedly regenerated by treatment with an oxygen containing gas for removal of carbonaceous matter without significant loss of catalyst activity. Still another object of the invention is to use a catalyst of great physical strength which may be employed in granular form without serious disintegration. Other ob- Jects will become apparentzfrom the following description. I

The catalyst which we employ is prepared in the following manner: A silicagel, so-called, is prepared by adding a solution of soluble silicate, for example, sodium silicate, to an excess of strong mineral acid, such as hydrochloric acid or sulfuric acid. e prefer to use sodium silicate solution containing about to of Nansiom. In this formula :1: is unity or greater. The acid employed in making the gel may suitably be ;about 15% to H2804 and an excess of 10% to 50% may suitably be employed. Other strong acids may be used, such as HCl, HNOa, etc. We have sometimes reversed this procedure, however, and added the acid to the silicate solution which causes immediate precipitation. This method gives a very active catalyst but one of low mechanical strength.

After adding the silicate solution to the acid, and mixing, it is allowed to stand and soon the solution solidifies to a jelly. This is broken up by agitation and 'washed in running water until substantially all the acid and soluble salts are removed. Considerable time is required to permit ,all the salts to diffuse from the pieces of jelly and the washing operation is facilitated by employing hot water or by digestion and boiling. The gel is then separated from the water and dried. It now resembles an irregular sand and at this stage it is crushed and screened to remove particles which are too fine for ultimate use. The gel so prepared is characterized by possessing a submicroscopic pore structure which provides an, enormous amount of pore surface accessible only to those materials which can freely penetrate the pores and gain access to the interior of the grains. If desired, the gel may be washed only partially at first, then partly dried and finally washed until the water gives no further test for acid ion. Also, the gel may be further washed with distilled water after final drying.

The next step in the preparation of the catalyst is to subject the gel to the action of a soluble salt of cerium under conditions such that a layer of insoluble cerium compound is deposited on the interior pore surface of the gel. Heretofore, attempts have been made to deposit metal compounds on silica gel but these attempts have usually not succeeded in accomplishing more than depositing the metal compound on the external surface of the silica gel grains. Because of the extremely small dimensions of the pores, these are apparently plugged by precipitates and great care must be exercised to prevent the formation of a heavy precipitate. This we avoid by maintaining the gel in a slightly acid condition and the presence of basic precipitating reagents is scrupulously avoided.

As an example of the method of making the catalyst, silica gel was prepared by diluting commercial water glass with an equal' volume of distilled water and adding, with stirring, hydrochloric acid of 5 N. concentration until about 20% of excess acid was present over that required to neutralize the water glass. The precipitated silica gel was then washed with hot distilled water until the washings tested free of chloride. About IOO'gra-ms of the moist precipitate was digested ,for two hours with about 3 liters of 0.1 molar cerium nitrate solution on a steam bath. This treatment causes a hydrolysis of the cerium nitrate accompanied by a deposition 'of acerium compound on the surface of the silica which we believe to be an adsorbed layer of active cerium compound on the surface of the silica on which it is deposited.

The treated silica was washed three times by decantation with distilled water followed by two washings of hot water and two washings of cold water on a suction funnel using about 300 ml. of water for each washing. The washed material was finally dried at 210 to 220 F. in a steam heated drying oven, after which it was ready for use as a catalyst for promoting cracking of gas oil. It is estimated that the amountof cerium in the dried catalyst was about 0.5 wt. percent. When activating the gel with cerium salt, we prefer to maintain the solution slightly acid corresponding to a hydrogen ion concentration of more effective but also yields a about 2-4 pH. The hydrogen ion concentration will usually increase during the activation treatment, for example, the pH may be 2.5 at the start and l to 1.5 at the end of the treatment.

We prefer to employ this catalyst for the cracking of hydrocarbon oils at temperatures of about 700 to 1050" F., employing contact times of between about /2 second to 5 minutes, preferably contact times within the range of 1 second to 1 minute. Contact time referred to is the time required for one volume of oil vapor at the condition of experiment to pass one volume of catalyst. We prefer to employ the catalyst at relatively low pressures, for example, atmospheric to 50 lbs. per square inch gage. However, somewhat higher pressures, e. g., 100 to 200 lbs. per square inch may be used.

As an example of the use of the cerium catalyst for the" cracking of heavy petroleum oils to gasoline, a six-hour run was made in which 35 A. P. I. Mid-Continent gas oil was vaporized in 'a coil, heated to 925 F. and passed through a bed of the catalyst. The pressure employed was atmospheric and the velocity was 1.2 volumes of oil per volume of catalyst space per hour, equal to 26.8 bbls. (42 gal.) per ton of catalyst per hour, or a time of contact of 8.5 seconds. The following yields were obtained from a single pass:

T Silica Catalyst 21332 Ett cerium Gas yield volume percent. 9. 55 16. 7 Gas loss .percent 1. 77 2. 34 Gas produced per gal. of gasoline .pounds l. 31 0. 99 Gasoline gravity .degrees A. P. I 58. 4 59. 4 Antlknock value 0. F R M. (determined by ends). l 72. 6 80. 4 Unsaturation .percent. 81. 0 84. 0

The above data show that the treatment of silica with cerium by the method employed in which the cerium is adsorbed from an acid solution produces a cracking catalyst which-is not only gasoline having a much higher knock rating.

The explanation of the enhanced effectiveness of the catalyst is not easily determined. We believe, however, that when the silica gel is treated with the cerium salt solution,.there occurs a simultaneous adsorption and hydrolysis causing the deposition of a cerium compound on the surface of the silica throughout its entire pore structure. This compound is probably an oxygen compound of cerium such as cerium hydroxide or more probably the cerium unites to form a complex compound with the SiOz molecules and hydrated SiOz molecules on the surface of the gel and within the pores of the grains thereof. It is believed that the molecules of SiOz at the surface present unsatisfied valences which form a chemical union with the cerium and its compounds so that the gel treated with cerium salt solution is substantially identical in physical structure with the untreated silica gel excepting that the entire surface, including the immense interior pore surface, is coated with not more than a monomolecular layer of cerium compound. Furthermore, we believe that the electronic structure of the cerium compound on the surface is disturbed by the unbalanced electronic structure of the balanced electronic structure, or to the molecular orientation of the cerium compound.

As evidence of the hydrolysis of the cerium salt on the surface of the gel, we find that the solution develops a definite acidity which can only be accounted for by the following hydrolytic reaction:

Ce(OH) 2- (S102) +2HNOa We choose to call this reaction, indicating that the hydrolysis or splitting of the cerium salt is brought about by the adsorption phenomenon. Simultaneously, with the formation of acid in the solution, there is deposited within the silica a measurable amount of cerium compound which we have shown by analy sis to vary between about 0.1 to 2% of cerium, depending partly on the concentration of cerium salt solution employed, the hydrogen ion concentration in the solution, and the method of treatment.

Although we prefer to use a cerium salt solution of about 0.1 molar concentration, this may be varied over a considerable range without greatly affecting the amount of cerium deposited within the gel. Thus, we may use concentrations from about 0.02 M. to 1.5 IVL, if desired. We may increase the amount of cerium hydrolyzed by various methods. For example, we may add a buffer salt to the solution; such as cerium acetate for the purpose of regulating the pH value of the solution, care being taken to avoid pH values which might result in the precipitation of insoluble cerium compounds by double decomposition. We may also repeat the treatment of the gel with cerium solution of the same or different concentrations, or we may perform the treatment in a flowing stream. The cerium salt solution may be made to flow through a series of beds of the gel in rotation so that the most nearly spent solution serves to contact the fresh gel, thus adsorbing the greater amount of the cerium from the solution.

In the previous description of the method of preparing the catalyst, the freshly prepared gel was dried after washing and before treating with the cerium solution. However, it is sometimes desirable to omit this drying step. The freshly made gel which has been thoroughly Washed may be immediately treated with the cerium solution and then dried. In this case, however, a longer SiOz, previously referred to as unsatisfied valence,

time is required for diffusion of the solution into the larger pieces of the jelly or precipitate.

As indicated above, the catalyst may be regenerated after it has become fouled with.carbonaceous deposits in the cracking operation. Regeneration is most conveniently accomplished by passing a stream of air and inert gas, for example, steam, through the catalyst bed, care being taken to control the oxygen concentration of the regenerating gas so that the combustion temperature is kept below about 1200 F. and preferably below about 1100 F. Excessive heating above these temperatures causes catalyst deterioration. After regeneration, the cracking may be continued. The duration of cracking between regeneration periods may be about 5 hours but, this depends largely on the nature of the stock being cracked. If the stock cracked is a residual oil containing asphaltic matter, the duration of cracking is considerably less before catalyst activity is seriously reduced. Thus, with a typical Mid-Continent residual oil of about 22 A. P. I. gravity, the catalyst may be used for a period of about 30 minutes to 2 hours between reaction an adsorbolytic I 'without heating to a regenerations. when using gas oil, we have found that in a typical operation the catalyst activity has decreased about 25% to 50% in a. period or 6 hours. In the case of residual oils or very heavy distillate charging. stocks, we may initially crack the oil in" one catalyst bed and produce intermediate boiling hydrocarbons with very little gasoline. Then we may pass the vapors directly into a second catalyst bed with or higher temperature to complete the cracking. The extent or depth of cracking per pass depends partly on the freshness of the catalyst and on the temperature. If desired, the process may be conducted to produce from gas oil about 45% to 55% of gasoline in a single pass and the uncracked products heavier than gasoline may be either recycled in the operation or cracked in a secondary crackin: operation. Alternatively, the extent of cracking may be maintained about 20 to 30% and the uncracked heavy products may be recycled until completely cracked, the only products being gasoline and gas. Carbonaceous matter produced in the operation, is deposited on the catalyst and removed in regeneration.

If desired, we may employ the catalyst in moving bed apparatus in which a portion of the spent catalyst is continuously withdrawn and regenerated externally, fresh and/or regenerated catalyst being supplied continuously to the apparatus. We may also employ the catalyst in finely divided form. For example, the catalyst may be finely divided by grinding and supplied as a slurry in oil to the cracking chamber or cell or introduced as a powder into the vapor stream.

'In this type of operation, the spent catalyst is settled or filtered from the products and separately regenerated,

Although we have given specific examples of methods of preparing the catalyst and have described its use in certain cracking operations, we intend that our invention be limited only by the following claims.

We claim:

1. The process of converting heavy hydrocarbon oils into gasoline, comprising subjecting the vapors of said oils at a temperature between about 700 and 1050 F, to the action of a catalyst consisting essentially of silica gel treated with a cerium compound in an acid solution and thereafter washed and dried.

2. The process of claim 1 wherein said silica gel is in hydrated form when treated with said cerium compound.

' 3. The process of converting heavy hydrocarbon oils into gasoline comprising subjecting the vapors of said oils at conversion temperature to I the action of a solid, conversion catalyst comprising silica gel promoted with a small amount of adsorbed cerium oxide containing between about 0.1 and 2% of cerium based on the weight of the said conversion catalyst.

- RALPH M. MELAVEN.

RODNEY V. SHANKLAND. 

